Diarylbutadiene-substituted diorganopolysiloxanes and photoprotective compositions comprised thereof

ABSTRACT

Novel 4,4-diarylbutadiene-substituted diorganopolysiloxanes having the structural formulae (1) or (2):  
                 
 
in which A is a radical of formula (3) below:  
                 
are useful sunscreens for UV-photoprotecting human skin against the damaging effects of UV-radiation, notably UV-A radiation.

CROSS-REFERENCE TO PRIORITY/PROVISIONAL APPLICATIONS

This application claims priority under 35 U.S.C. § 119 of FR 03/50900,filed Nov. 25, 2003, and of provisional application Ser. No. 60/526,987,filed Dec. 5, 2003, each hereby expressly incorporated by reference andeach assigned to the assignee hereof. This application is also acontinuation of said '987 provisional.

BACKGROUND OF THE INVENTION

1. Technical Field of the Invention

The present invention relates to novel diorganosiloxane compoundscontaining a 4,4-diarylbutadiene functional group.

The present invention also relates to the formulation of thesediorganosiloxane compounds containing a 4,4-diarylbutadiene functioninto cosmetic compositions useful for screening out UV-A radiation.

This invention also relates to photoprotective compositions comprisingdiorganosiloxane compounds containing a 4,4-diarylbutadiene function, assunscreens that are active in the field of UV radiation and moreparticularly in the field of UV-A rays.

2. Description of Background and/or Related and/or Prior Art

It is known that radiation with wavelengths of from 280 nm to 400 nmpermits tanning of the human epidermis and that radiation withwavelengths of from 280 to 320 nm, which is known as UV-B radiation,causes skin burns and erythema that may be harmful to the development ofa natural tan. For these reasons and also for aesthetic reasons, thereis increasing demand for means for controlling this natural tanning.This UV-B radiation should thus be screened out.

It is also known that UV-A rays, with wavelengths of between 320 and 400nm, which cause browning of the skin, are liable to induce impairment inthe skin, especially in the case of sensitive skin and/or skin that iscontinually exposed to sunlight. UV-A rays in particular result in aloss of elasticity of the skin and the appearance of wrinkles, leadingto premature aging of the skin. They promote triggering of the erythemalreaction or amplify this reaction in the case of certain individuals andmay even be the cause of phototoxic or photoallergic reactions. Thus,for aesthetic and cosmetic reasons such as the conservation of thenatural elasticity of the skin, more and more individuals wish tocontrol the effect of UV-A rays on their skin. It is thus desirable alsoto screen out UV-A radiation.

There is at the present time an ever-increasing need for aromaticcompounds that are effective at screening out UV-A radiation andpreferably in the range from 340 to 400 nm (range known as long UV-A orUV-A-1). Besides their good photoprotective efficacy in this range, thedesired UV-A screening agents should have good cosmetic properties, goodsolubility in the usual solvents and in particular in fatty substancessuch as oils and fats, good resistance to water and to perspiration(remanence) and also satisfactory photostability.

A limited number of organic compounds that are effective towards UV-Arays and especially long UV-A rays are currently available on theUV-screening agent market.

In this regard, one family of UV-A screening agents that is particularlyeffective in the UV-A range currently includes dibenzoylmethanederivatives, and especially 4-tert-butyl-4′-methoxydibenzoylmethane,which specifically have good intrinsic absorbing power. Thesedibenzoylmethane derivatives, which are now products that are well knownper se as screening agents active in the UV-A range, are describedespecially in FR-A-2,326,405 and FR-A-2,440,933, and also inEP-A-0-114,607; 4-tert-butyl-4′-methoxydibenzoylmethane is moreovercurrently sold under the trademark “Parsol 1789” by Hoffmann LaRoche.

Unfortunately, it transpires that dibenzoylmethane derivatives areproducts that are relatively photosensitive to UV-A radiation, i.e.,more specifically, they have an annoying tendency to be degraded more orless quickly by the action of this radiation. Thus, this substantiallack of photochemical stability of dibenzoylmethane derivatives withrespect to ultraviolet radiation, to which they are by nature intendedto be subjected, does not make it possible to ensure constant protectionduring prolonged exposure to the sun, and as a result the user needs tomake repeated applications at regular and short intervals in order toobtain effective protection of the skin against UV rays.

Another difficulty, which is independent of the one mentioned above,encountered with dibenzoylmethane derivatives is that they arelipophilic screening agents that have the particular feature but alsothe drawback of being solid at room temperature. As a result, their usein an antisun or sunscreen cosmetic composition entails certainconstraints as regards their formulation and application, in particularwhen it is a matter of finding solvents for dissolving them correctly,alone or in combination with other screening agents.

Thus, need continues to exist for novel families of aromatic compoundsthat are effective in terms of screening in the UV-A range andespecially the long UV-A range, but which are photostable and also havegood solubility in the usual solvents, good cosmetic properties and alsogood resistance to water and to perspiration (remanence).

SUMMARY OF THE INVENTION

Surprisingly, a novel family of diorganosiloxane compounds containing a4,4-diarylbutadiene functional group has now been developed whichameliorates or avoids the above disadvantages and drawbacks of the priorart.

The present invention thus features a novel family of diorganosiloxanecompounds containing a 4,4-diarylbutadiene function of general formula(1) or (2) more fully described hereinbelow.

This invention also features the formulation of at least onediorganosiloxane compound containing a 4,4-diarylbutadiene function ofgeneral formula (1) or (2) into cosmetic or dermatological compositionsuseful for screening out rays with wavelengths of from 320 to 400 nm.

The present invention accordingly features photoprotective compositionscomprising at least one diorganosiloxane compound containing a4,4-diarylbutadiene function of general formula (1) or (2) more fullydescribed hereinbelow.

The diorganosiloxane compounds containing a 4,4-diarylbutadienefunction, in accordance with the invention, are in isolated form or inthe form of a mixture and correspond to one of the general formulae (1)or (2) below:

in which A is a radical of formula (3) below:

in which the radicals R₁, which may be identical or different, are eacha hydroxyl radical, a saturated or unsaturated, linear or branchedC₁-C₁₀ alkyl radical, a saturated or unsaturated, linear or branchedC₁-C₁₀ alkoxy radical, with the proviso that two adjacent groups R₁ maytogether form a C₁-C₃ alkylenedioxy ring; n is an integer ranging from 0to 2; the radical Z is hydrogen, —(C═O)OR₂, —(C═O)R₃, —(C═O)NR₄R₅,—SO₂R₆, —CN or —(C═O)—X-L; X is —O— or —NR₄—; L is a divalent radicalattaching the radical A to the silicone chain and corresponding to oneof the formulae (a), (a′) or (a″) below:

in which W is a saturated or unsaturated, linear or branched C₁-C₆alkylene radical, optionally substituted with a hydroxyl radical or asaturated or unsaturated, linear or branched C₁-C₈ alkyl radical; Y is ahydrogen atom, a hydroxyl radical or a saturated or unsaturated, linearor branched C₁-C₈ alkyl radical; p is 0 or 1; the radicals R, which maybe identical or different, are each a saturated or unsaturated, linearor branched C₁-C₂₀ alkyl radical, a phenyl radical, a3,3,3-trifluoropropyl radical or a trimethylsilyloxy radical, at least80% in numerical terms of the radicals R being methyl radicals; theradicals B, which may be identical or different, are each a radical R ora radical A; r is a number ranging from 0 to 50; s is a number rangingfrom 0 to 20 and, if s is 0, at least one of the two radicals B is aradical A; u is a number ranging from 1 to 6 inclusive; t is a numberranging from 0 to 10; t+u is greater than or equal to 3; the radical R₂is hydrogen or a saturated or unsaturated, linear or branched C₁-C₂₀alkyl radical; the radical R₃ is a saturated or unsaturated, linear orbranched C₁-C₂₀ alkyl radical or a C₆-C₁₂ aryl radical; the radicals R₄and R₅, which may be identical or different, are each hydrogen or asaturated or unsaturated, linear or branched C₁-C₂₀ alkyl radical; andthe radical R₆ is a saturated or unsaturated, linear or branched C₁-C₂₀alkyl radical or a C₆-C₁₂ aryl radical, with the proviso that when twogroups (C═O)—X-L- are present, L is bonded to only one group A or B offormula (1) or (2): i.e., s=1 with B being other than A or s=0 and onlyone B is A for formula (1) and u=1 for formula (2).

DETAILED DESCRIPTION OF BEST MODE AND SPECIFIC/PREFERRED EMBODIMENTS OFTHE INVENTION

Although, in formula (3) above, only the isomers in which thesubstituent Z is in the cis position relative to the diaryl substituentare represented, this formula should be understood as also including thecorresponding trans isomer.

In formulae (1) and (2) above, the alkyl radicals may be linear orbranched, saturated or unsaturated and selected especially from amongmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl,n-amyl, isoamyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl andtert-octyl radicals. The alkyl radical that is particularly preferred isthe methyl radical.

In formula (3) above, the alkoxy radicals may be linear or branched andselected especially from among methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy and isobutoxy radicals. The alkoxy radical that is particularlypreferred is the methoxy radical.

In formula (1) above, the aryl radicals are preferably phenyl.

The linear or cyclic diorganosiloxanes of formula (1) or (2) within thescope of the present invention are oligomers or random polymerspreferably satisfying at least one, and even more preferably all, of thefollowing characteristics:

-   -   the radical Z is —(C═O)R₃, —CN or —(C═O)—X-L-;    -   R₃ is a C₁-C₄ alkyl radical and even more preferably ethyl;    -   R is C₁-C₄ alkyl and even more preferably methyl;    -   B is C₁-C₄ alkyl and even more preferably methyl (in the case        where the compound is of formula (1));    -   r ranges from 0 to 10 inclusive; s ranges from 0 to 6 inclusive        (in the case where the compound is of formula (1));    -   t+u ranges from 3 to 5 (in the case where the compound is of        formula (2));    -   n is 0;    -   W is CH₂;    -   p is 1;    -   Y is H or CH₃.

Among the preferred diorganosiloxanes of formula (1), the compounds A,B, C, D and E having the following formulae are representative:

One family of diorganosiloxane compounds containing a4,4-diarylbutadiene function of formula (1) or (2) that are particularlypreferred are those in which Z is —CN. These particular compounds areeffective in the range of long UV-A rays (340400 nm).

Among these compounds, the ones that are the preferred are thosesatisfying at least one of the following characteristics and even morepreferably all of the following characteristics:

-   -   R is C₁-C₄ alkyl and even more preferably methyl;    -   B is C₁-C₄ alkyl and even more preferably methyl (in the case        where the compound is of formula (1));    -   r ranges from 0 to 10 inclusive; s ranges from 0 to 6 inclusive        (in the case where the compound is of formula (1));    -   t+u ranges from 3 to 5 (in the case where the compound is of        formula (2));    -   n is 0;    -   W is CH₂;    -   p is 1;    -   Y is H or CH₃.

Among these compounds of formula (1), the ones that are even moreparticularly preferred are the compounds F, G, H, I and J below:

To prepare the derivatives of formula (1) or (2), a conventional processmay be performed, by carrying out a hydrosilylation reaction startingwith the corresponding siloxane derivative in which, for example, allthe radicals A are hydrogen atoms. This derivative is referred tohereinbelow as the S1H-containing derivative and the correspondingsynthetic route is referred to as (Route 1).

The SiH groups may be present in the chain and/or at the ends of thechain. These S1H-containing derivatives are products that are well knownin the silicone industry and are generally commercially available. Theyare described, for example, in U.S. Pat. Nos. 3,220,972, 3,697,473 and4,340,709.

The S1H-containing derivatives corresponding, respectively, to thecompounds of formulae (1) and (2) may thus be represented by formulae(4) and (5) below:

in which:

-   -   R, r, s, t and u are as defined above for formulae (1) and (2),    -   B′, which may be identical or different, are each a radical R or        a hydrogen atom.

In order to prepare the siloxane compounds of the invention of formula(1) or (2) above, the process is performed in the following manner:(Scheme 1): on the S1H-containing derivative of corresponding formula(4) or (5), a hydrosilylation reaction is performed in the presence of acatalytically effective amount of a platinum catalyst on a4,4-diarylbutadiene organic derivative of formula (6) below:

in which R₁, Z, X and n have the same meaning as in formula (3) aboveand L′ corresponds to one of the two formulae (b) and (b′) below:

in which Y, W and p have the same meanings as in formulae (a), (a′) and(a″) above.

The hydrosilylation reaction is thus performed according to one of thefollowing two reactions:

The derivatives of formula (6) are obtained by Knoevenagel condensationof a β-phenylcinnamaldehyde derivative on a derivative of formula (7) asdescribed in EP-916,335:

in which the radicals R₁, Z, X, L′ and n have the same meaning as informulae (3) and (6) above.

The derivatives of formula (7) are obtained by alkylation of thecorresponding acid derivatives with corresponding alkene or alkynehalides.

As derivatives of the type Z-CH₂—X-L′, mention may be made of diallylmalonate (RN 1797-75-7), allyl cyanoacetate (RN 13361-32-5) or2-propenyl acetoacetate (RN 1118-84-9), which are commercial products.

In the case of the diorganosiloxane amide derivatives (X representsNR₃), another synthetic route (Route 2) for obtaining the compounds offormula (1) or (2) entails reacting a β-phenylcinnamaldehyde derivativewith an aminodiorganosiloxane of formula (8) below:

in which the radicals R₁, Z, R₃ and n have the same meaning as in theabove formulae and L″ corresponds to formula (c) below:

in which Y, W and p have the same meanings as in formula (a) above.

These derivatives (8) may be obtained by condensation of an acidchloride on the amino diorganosiloxanes of formula (9) below:

in which Z, R₃ and L″ have the same meanings as in the above formulae.

As derivatives of the type Z-CH₂—COCl, mention may be made ofcyanoacetyl chloride or monoethylmalonic acid chloride, which arecommercial products.

The preparation of the aminosiloxanes of formula (9) is described, forexample, in GB-185,984. As aminosiloxanes that are particularly suitablefor preparing the compounds according to the invention, mention may bemade of aminopropylheptamethyltrisiloxane,aminoisobutylheptamethyltrisiloxane or trimethylsilylamodimethiconessuch as: the product sold under the trademark “X2-8260” by Dow Corning,with an amine number of 2.8 meq/g; the product sold under the trademark“SLM 55051/3” by Wacker, with an amine number of 0.47 meq/g; C₁₂dimethylalkyl PDMSs, such as the product sold under the trademark “SLM23046/1” by Wacker, with an amine number of 1.2 meq/gram; α,ω-trimethylpolymethyl(fatty)alkyl arylalkylsiloxanes, such as the product soldunder the trademark “SLM 23056/2” by Wacker, with an amine number of 1.3meq/gram; PDMSs in which the NH₂ radical is in an α and ω positionrelative to an alkyl site, such as the products sold under thetrademarks “Tegomer A-SI 2120” with an amine number of 1.95 meq/g and“Tegomer A-SI 2320” with an amine number of 0.86 meq/gram, byGoldschmidt.

The preparation of the cyclic aminosiloxanes is described, for example,in the article by A. Kopylov, Zh. Obshch. Khim., 54(2), 367-71 (1984).

The compounds of formula (I) are generally present in the compositionsof the invention in proportions of between 0.01% and 20% by weight andpreferably between 0.1% and 10% by weight relative to the total weightof the composition.

The compositions in accordance with the invention may also compriseother additional UV-A-active and/or UV-B-active organic or mineralUV-screening agents that are water-soluble, liposoluble or eveninsoluble in the cosmetic solvents commonly used.

The additional organic screening agents are selected especially fromamong the anthranilates; cinnamic derivatives; dibenzoylmethanederivatives; salicylic derivatives; camphor derivatives; triazinederivatives such as those described in U.S. Pat. No. 4,367,390,EP-863,145, EP-517,104, EP-570,838, EP-796,851, EP-775,698, EP-878,469,EP-933,376, EP-507,691, EP-507,692, EP-790,243, EP-944,624; benzophenonederivatives; β,β-diphenylacrylate derivatives; benzotriazolederivatives; benzalmalonate derivatives; benzimidazole derivatives;imidazolines; bis-benzazolyl derivatives as described in EP-669,323 andU.S. Pat. No. 2,463,264; p-aminobenzoic acid (PABA) derivatives;methylenebis(hydroxyphenylbenzotriazole) derivatives as described inU.S. Pat. Nos. 5,237,071, 5,166,355, GB-2-303,549, DE-197,26,184 andEP-893,119; benzoxazole derivatives as described in EP-0-832,642,EP-1-027,883, EP-1-300,137 and DE-101,62,844; screening polymers andscreening silicones other than those of formula (1) or (2) such as thosedescribed especially in patent application WO 93/04665;α-alkylstyrene-based dimers, such as those described in DE-198,55,649;non-siliceous 4,4-diarylbutadienes such as those described inEP-0-967,200, DE-197,46,654, DE-197,55,649, EP-A-1-008586, EP-1-133,980and EP-133,981, and mixtures thereof.

As examples of additional organic screening agents, mention may be madeof those denoted hereinbelow under their INCI name:

Para-Aminobenzoic Acid Derivatives:

-   PABA,-   Ethyl PABA,-   Ethyl dihydroxypropyl PABA,-   Ethylhexyl dimethyl PABA sold in particular under the name “Escalol    507” by ISP,-   Glyceryl PABA,-   PEG-25 PABA sold under the name “Uvinul P25” by BASF.

Salicylic Derivatives:

-   Homosalate sold under the name “Eusolex HMS” by Rona/EM Industries,-   Ethylhexyl salicylate sold under the name “Neo Heliopan OS” by    Haarmann and Reimer,-   Dipropylene glycol salicylate sold under the name “Dipsal” by Scher,-   TEA salicylate sold under the name “Neo Heliopan TS” by Haarmann and    Reimer.

Dibenzoylmethane Derivatives:

-   Butyl methoxydibenzoylmethane sold in particular under the trademark    “Parsol 1789” by Hoffmann LaRoche,-   Isopropyldibenzoylmethane.

Cinnamic Derivatives:

-   Ethylhexyl methoxycinnamate sold in particular under the trademark    “Parsol MCX” by Hoffmann LaRoche,-   Isopropyl methoxycinnamate,-   Isoamyl methoxycinnamate sold under the trademark “Neo Heliopan E    1000” by Haarmann and Reimer,-   Cinoxate,-   DEA methoxycinnamate,-   Diisopropyl methylcinnamate,-   Glyceryl ethylhexanoate dimethoxycinnamate.

β,β′-Diphenylacrylate Derivatives:

-   Octocrylene sold in particular under the trademark “Uvinul N539” by    BASF,-   Etocrylene sold in particular under the trademark “Uvinul N35” by    BASF.

Benzophenone Derivatives:

-   Benzophenone-1 sold under the trademark “Uvinul 400” by BASF,-   Benzophenone-2 sold under the trademark “Uvinul D50” by BASF,-   Benzophenone-3 or Oxybenzone sold under the trademark “Uvinul M40”    by BASF,-   Benzophenone-4 sold under the trademark “Uvinul MS40” by BASF,-   Benzophenone-5,-   Benzophenone-6 sold under the trademark “Helisorb 11” by Norquay,-   Benzophenone-8 sold under the trademark “Spectra-Sorb UV-24” by    American Cyanamid,-   Benzophenone-9 sold under the trademark “Uvinul DS49” by BASF,-   Benzophenone-12,-   n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate.

Benzylidenecamphor Derivatives:

-   3-Benzylidenecamphor manufactured under the name “Mexoryl SD” by    Chimex,-   4-Methylbenzylidenecamphor sold under the name “Eusolex 6300” by    Merck,-   Benzylidenecamphorsulfonic acid manufactured under the name “Mexoryl    SL” by Chimex,-   Camphor benzalkonium methosulfate manufactured under the name    “Mexoryl SO” by Chimex,-   Terephthalylidenedicamphorsulfonic acid manufactured under the name    “Mexoryl SX” by Chimex,-   Polyacrylamidomethylbenzylidenecamphor manufactured under the name    “Mexoryl SW” by Chimex.

Phenylbenzimidazole Derivatives:

-   Phenylbenzimidazolesulfonic acid sold in particular under the    trademark “Eusolex 232” by Merck,-   Disodium phenyl dibenzimidazole tetrasulfonate sold under the    trademark “Neo Heliopan AP” by Haarmann and Reimer.

Triazine Derivatives:

-   Anisotriazine sold under the trademark “Tinosorb S” by Ciba Geigy,-   Ethylhexyltriazone sold in particular under the trademark “Uvinul    T150” by BASF,-   Diethylhexylbutamidotriazone sold under the trademark “UV-Asorb HEB”    by Sigma 3V.

Phenylbenzotriazole Derivatives:

-   Drometrizole trisiloxane sold under the name “Silatrizole” by Rhodia    Chimie,-   Methylenebis(benzotriazolyl)tetramethylbutylphenol sold in solid    form under the trademark “Mixxim BB/100” by Fairmount Chemical, or    in micronized form as an aqueous dispersion under the trademark    “Tinosorb M” by Ciba Specialty Chemicals.

Anthranilic Derivatives:

-   Menthyl anthranilate sold under the trademark “Neo Heliopan MA” by    Haarmann and Reimer.

Imidazoline derivatives:

-   Ethylhexyldimethoxybenzylidenedioxoimidazoline propionate.

Benzalmalonate Derivatives:

-   Polyorganosiloxane containing a benzalmalonate function, such as the    product Polysilicone-15 sold under the trademark “Parsol SLX” by    Hoffmann LaRoche.

Non-siliceous 4,4-diarylbutadiene Derivatives:

-   1,1-Dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene.

Benzoxazole Derivatives:

-   2,4-Bis[5-1    (dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine    sold under the name UV-Asorb K2A by Sigma 3V,    and mixtures thereof.

The additional organic UV-screening agents that are preferred are:

-   Ethylhexyl salicylate,-   Ethylhexyl methoxycinnamate,-   Butyl methoxydibenzoylmethane,-   Octocrylene,-   Phenylbenzimidazolesulfonic acid,-   Benzophenone-3,-   Benzophenone-4,-   Benzophenone-5,-   n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,-   4-Methylbenzylidenecamphor,-   Terephthalylidenedicamphorsulfonic acid,-   Disodium phenyldibenzimidazoletetrasulfonate,-   Anisotriazine,-   Ethylhexyltriazone,-   Diethylhexylbutamidotriazone,-   Methylenebis(benzotriazolyl)tetramethylbutylphenol,-   Drometrizole trisiloxane,-   Polysilicone-15,-   1,1-Dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene,-   2,4-Bis[5-1    (dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine    and mixtures thereof.

The additional mineral screening agents are selected from among pigmentsor even nanopigments (mean size of the primary particles: generallybetween 5 nm and 100 nm and preferably between 10 nm and 50 nm) ofcoated or uncoated metal oxides such as, for example, nanopigments oftitanium oxide (amorphous or crystallized in rutile and/or anataseform), of iron oxide, of zinc oxide, of zirconium oxide or of ceriumoxide and mixtures thereof which are all UV photoprotective agents thatare well known per se. Standard coating agents are, moreover, aluminaand/or aluminum stearate. Such coated or uncoated metal oxidenanopigments are described in particular in EP-518,772 and EP-518,773.

The additional UV-screening agents in accordance with the invention aregenerally present in the compositions according to the invention inproportions ranging from 0.01% to 20% by weight relative to the totalweight of the composition, and preferably ranging from 0.1% to 10% byweight relative to the total weight of the composition.

The cosmetic compositions according to the invention may also containagents for artificially tanning and/or browning the skin (self-tanningagents) such as dihydroxyacetone (DHA). They are preferably present inamounts ranging from 0.1% to 10% and more preferably from 0.2% to 8% byweight relative to the total weight of the composition.

The compositions in accordance with the present invention may alsocomprise standard cosmetic adjuvants selected especially from amongfatty substances, organic solvents, ionic or nonionic thickeners,softeners, humectants, antioxidants, moisturizers, desquamating agents,free-radical scavengers, antipollution agents, antibacterial agents,anti-inflammatory agents, depigmenting agents, propigmenting agents,opacifiers, stabilizers, emollients, silicones, antifoams, insectrepellents, fragrances, preservatives, anionic, cationic, nonionic,zwitterionic or amphoteric surfactants, substance P antagonists,substance CGRP antagonists, fillers, pigments, polymers, propellants,acidifying or basifying agents, or any other ingredient usually used incosmetics and/or dermatology.

The fatty substances may be an oil or a wax or mixtures thereof. Theterm “oil” means a compound that is liquid at room temperature. The term“wax” means a compound that is solid or substantially solid at roomtemperature, and whose melting point is generally above 35° C.

Oils that may be mentioned include mineral oils (paraffin); plant oils(sweet almond oil, macadamia oil, blackcurrant pip oil or jojoba oil);synthetic oils, for instance perhydrosqualene, fatty alcohols, fattyacids or fatty esters (for instance the C₁₂-C₁₅ alkyl benzoate soldunder the trademark “Finsolv TN” by Witco, octyl palmitate, isopropyllanolate, triglycerides, including capric/caprylic acid triglycerides,oxyethylenated or oxypropylenated fatty esters and ethers; silicone oils(cyclomethicone and polydimethylsiloxanes or PDMS) or fluoro oils, andpolyalkylenes.

Waxy compounds that may be mentioned include paraffin, carnauba wax,beeswax and hydrogenated castor oil.

Among the organic solvents that may be mentioned are lower alcohols andpolyols. These lower polyols may be chosen from glycols and glycolethers, for instance ethylene glycol, propylene glycol, butylene glycol,dipropylene glycol or diethylene glycol.

The thickeners may be chosen especially from among crosslinked acrylicpolymers, for instance carbomers, acrylate/C₁₀-C₃₀ alkylacrylatecrosslinked polymers of the type such as Pemulen or polyacrylate-3 soldunder the name Viscophobe DB 1000 by Amerchol; polyacrylamides such asthe polyacrylamide, C₁₃-C₁₄ isoparaffin and laureth-7 emulsion soldunder the name Sepigel 305 by SEPPIC, AMPS homopolymers or copolymerssuch as Hostacerin AMPS sold by Clariant, modified or unmodified guargums and celluloses, such as hydroxypropyl guar gum,methylhydroxyethylcellulose and hydroxypropylmethylcellulose, xanthangum, and nanometric silicas of the Aerosil type.

Needless to say, one skilled in the art will take care to select theoptional additional compound(s) mentioned above and/or the amountsthereof such that the advantageous properties intrinsically associatedwith the compounds in accordance with the invention are not, or are notsubstantially, adversely affected by the envisaged addition(s).

The compositions according to the invention may be prepared according totechniques that are well known to those skilled in the art, inparticular those intended for the preparation of emulsions ofoil-in-water or water-in-oil type.

This composition may be in particular in the form of a simple or complexemulsion (O/W, W/O, O/W/O or W/O/W emulsion) such as a cream or a milk,in the form of a gel or a cream-gel, or in the form of a lotion, an oil,a powder or a solid tube, and may optionally be packaged as an aerosoland may be in the form of a mousse or a spray.

The compositions according to the invention are preferably in the formof an oil-in-water or water-in-oil emulsion.

When it is an emulsion, the aqueous phase of this emulsion may comprisea nonionic vesicular dispersion prepared according to known processes(Bangham, Standish and Watkins, J. Mol. Biol., 13, 238 (1965),FR-2,315,991 and FR-2,416,008).

When the cosmetic composition according to the invention is used to carefor the human epidermis, it may be in the form of a suspension or adispersion in solvents or fatty substances, in the form of a nonionicvesicular dispersion or in the form of an emulsion, preferably ofoil-in-water type, such as a cream or a milk, or in the form of anointment, a gel, a cream-gel, an antisun oil, a solid tube, a powder, anaerosol mousse or a spray.

When the cosmetic composition according to the invention is used forhaircare, it may be in the form of a shampoo, a lotion, a gel, anemulsion or a nonionic vesicular dispersion and may constitute, forexample, a rinse-out composition, to be applied before or aftershampooing, before or after dyeing or bleaching, or before, during orafter permanent-waving or relaxing the hair, a styling or treatinglotion or gel, a blow-drying or hairsetting lotion or gel, or acomposition for permanent-waving, relaxing, dyeing or bleaching thehair.

When the composition is used as a makeup product for the nails, thelips, the eyelashes, the eyebrows or the skin, such as an epidermaltreatment cream, a foundation, a tube of lipstick, an eyeshadow, amakeup rouge, a mascara or an eyeliner, it may be in solid or pasty,anhydrous or aqueous form, such as oil-in-water or water-in-oilemulsions, nonionic vesicular dispersions or suspensions.

The present invention also features formulation of a compound of formula(1) or (2) into cosmetic compositions as an agent for controlling thevariation in the color of the skin caused by UV-A radiation.

This invention also features the use of a compound of formula (1) asdefined above as an agent for photostabilizing synthetic polymers suchas plastics or lenses, in particular spectacle lenses or contact lenses.

In order to further illustrate the present invention and the advantagesthereof, the following specific examples are given, it being understoodthat same are intended only as illustrative and in nowise limitative. Insaid examples to follow, all parts and percentages are given by weight,unless otherwise indicated.

PREPARATION EXAMPLES Example 1 Preparation of Monoethylmono-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]-2-methylpropyl2-(3,3-diphenylprop-2-enylene)malonate (Via Route 1)

First Step: Preparation of Monoethyl Monomethallyl Malonate

A mixture of the potassium salt of monoethyl malonic acid (17 g, 0.1mol) and methallyl chloride (9.8 ml, 0.1 mol) in 150 ml of DMF ismaintained at 50° C. for four hours in a reactor. The mineral salts arefiltered off on a sinter funnel and the DMF is evaporated off underreduced pressure. The mixture is taken up in 100 ml of ethyl acetate.The organic phase is washed three times with water. The organic phase isdried over sodium sulfate and concentrated under reduced pressure. 16 gof a pale yellow oil are obtained, and are purified by fractionaldistillation. The fractions distilling at 58° C. under a vacuum of 0.1hPa are recovered in the form of a colorless oil (8 g, 40% yield) ofmonoethyl monomethallyl malonate, which is used without furtherpurification in the following step.

Second Step: Preparation of Monoethyl monomethallyl2-(3,3-diphenylprop-2-enylene)malonate

β-Phenylcinnamaldehyde (2 g, 0.0096 mol) is dissolved in 50 ml ofisopropanol in a reactor. 0.24 ml of the piperidine and the derivativefrom the first step (1.97 g, 0.011 mol) are added thereto. The reactionmixture is heated at 60° C. for 2 hours 30 minutes. The isopropanol isremoved under reduced pressure. After crystallization from heptane, thederivative monoethyl monomethallyl2-(3,3-diphenylprop-2-enylene)malonate (2.05 g, 57% yield) is obtainedin the form of a pale yellow powder:

¹H NMR (400 MHz): presence of the two E, Z isomers in a 4:1 ratio.

m.p. 95° C.

Third Step: Preparation of the Derivative of Example 1

A solution of the above product (1 g, 0.0026 mol) and of catalyst(complex containing 3-3.5% by weight of Pt in cyclovinylmethylsiloxanefrom Hüls Petrarch PC085: 40 μl) in 30 ml of toluene is heated to 80° C.0.65 g (0.029 mol) of heptamethyltrisiloxane is added dropwise theretoover 20 minutes. The solvent is evaporated off under vacuum. The oilobtained is purified by chromatography on a column of silica (eluent:CH₂Cl₂/heptane). The clean fractions of the derivative of Example 1 arerecovered (0.5 g, 31% yield) in the form of a pale yellow oil:

¹H NMR (400 MHz): presence of the two E, Z isomers in a 4:1 ratio.

UV (Ethanol) λ_(max)=333 nm, ε_(max)=39 530 E1%=660

Example 2 Preparation of the Random Derivative of Formula (1): s=6, r=6,B=CH₃, R=CH₃, n=0, Z=—COOEt, X=O, L of formula (a): Y=CH₃, p=1, W=CH₂(via Route 1):

A solution of the above product (1 g, 0.0026 mol) and of catalyst(complex containing 3-3.5% by weight of Pt in cyclovinylmethylsiloxanefrom Hüls Petrarch PC085: 40 μl) in 30 ml of toluene is heated to

90° C. 0.42 g (2.5 meq of S1H) of random copolymer (50-55%)methylhydro—(45-50%) dimethylsiloxane (PS122.5 from Petrarch) is addedthereto. The mixture is heated at 90° C. until the band at 2180 cm⁻¹ ininfrared has disappeared (i.e., ten hours). The solvent is evaporatedoff under vacuum. The oil obtained is washed twice with 80% ethanol. Thepale yellow oil obtained is taken up in dichloromethane, dried oversodium sulfate and passed through a bed of silica. After evaporating offthe solvent, clean fractions of the derivative of Example 2 (0.8 g, 56%yield) are obtained in the form of a pale yellow oil:

UV (Ethanol) λ_(max)=333 nm E1%=590.

Example 3 Preparation of3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl2-cyano-5,5-diphenylpenta-2,4-dienoate (Via Route 1)

First Step: Preparation of Allyl2-cyano-5,5-diphenylpenta-2,4-dienepentanoate

β-Phenylcinnamaldehyde (4 g, 0.0192 mol) is dissolved in 100 ml ofisopropanol in a reactor. 0.5 ml of piperidine and allyl cyanoacetate(2.64 g, 0.021 mol) are added thereto. The reaction mixture is heated at60° C. for 2 hours 30 minutes. The solution is concentrated underreduced pressure. The excess malonate is removed by distillation under avacuum of 0.02 hPa. After purification by chromatography on a column ofsilica (eluent: 95/5 heptane/EtOAc), clean fractions of the derivativeallyl 2-cyano-5,5-diphenylpenta-2,4-dienepentanoate (2.34 g, 77% yield)are obtained in the form of a pale yellow powder, which is used withoutfurther purification in the following step.

Second Step: Preparation of the Derivative of Example 3

A solution of the above product (1 g, 0.00317 mol) and of catalyst(complex containing 3-3.5% by weight of Pt in cyclovinylmethylsiloxanefrom Hüls Petrarch PC085: 40 μl) in 30 ml of toluene is heated to 80° C.0.776 g (0.0349 mol) of heptamethyltrisiloxane is added dropwise theretoover 20 minutes. The mixture is heated at 80° C. for 20 hours. Thesolvent is evaporated off under vacuum. The oil obtained is purified bychromatography on a column of silica (eluent: CH₂Cl₂/heptane). The cleanfractions of the derivative of Example 3 are recovered (0.93 g, 55%yield) in the form of a pale yellow oil:

UV (Ethanol) λ_(max)=358 nm, ε_(max)=30 874E1%=574

Example 4 Preparation of the Random Derivative of Formula (1): s=6, r=6,B=CH₃, R=CH₃, n=0, Z=—CN, X=O, L of formula (a): Y=H, p=1, W=CH₂ (ViaRoute 1)

A solution of the above product (1 g, 0.00317 mol) and of catalyst(complex containing 3-3.5% by weight of Pt in cyclovinylmethylsiloxanefrom Hüls Petrarch PC085: 40 pl) in 30 ml of toluene is heated to 90° C.0.52 g (3.1 meq of S1H) of the random copolymer (50-55%)methylhydro—(45-50%) dimethylsiloxane (PS122.5 from Petrarch) is addedthereto. The mixture is heated at 90° C. until the band at 2180 cm⁻¹ ininfrared has disappeared (i.e., 12 hours). The solvent is evaporated offunder vacuum. The oil obtained is washed twice with 80% ethanol. Thepale yellow oil obtained is taken up in dichloromethane, dried oversodium sulfate and passed through a bed of silica. After evaporating offthe solvent, the clean fractions of the derivative of Example 4 (1.06 g,62% yield) are obtained in the form of a pale yellow oil: UV (Ethanol)λ_(max) = 359 nm, E1% = 660.

Example 5 Preparation ofN-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-2-cyano-5,5-diphenylpenta-2,4-dienamide(Via Route 2)

First Step: Preparation ofcyano-N-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]acetamide

Cyanoacetyl chloride (5.2 g, 0.05 mol) is added dropwise over 20 minutesto a mixture of3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propylamine(13.93 g, 0.05 mol) and of triethylamine (5 g, 0.05 mol) in 40 ml ofdichloromethane. The temperature rises to 32° C. The mixture is refluxedfor two hours. The reaction mixture is poured into 150 ml of water andis extracted with dichloromethane. The organic phases are washed withwater and dried over sodium sulfate, and the solvent is then evaporatedoff. After purification by passing through a column of silica (eluent:70/30 heptane/ethyl acetate), 12.2 g (70% yield) ofcyano-N-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]acetamideare obtained in the form of a colorless oil, which is used withoutfurther purification in the following step.

Second Step: Preparation of the Derivative of Example 5

β-Phenylcinnamaldehyde (0.6 g, 2.88×10⁻³ mol) is dissolved in 30 ml ofisopropanol in a reactor. 0.1 ml of piperidine and the derivative fromthe preceding step (1 g, 2.88×10⁻³ mol) are added thereto. The reactionmixture is heated at 50° C. for 1 hour 30 minutes. The solution isconcentrated under reduced pressure. After purification bychromatography on a column of silica (eluent: 90/10 heptane/EtOAc), theclean fractions of the derivative of the example (0.95 g, 61% yield) areobtained in the form of a pale yellow oil:

UV (Ethanol) λ_(max)=351 nm, ε_(max)=27 650, E1%=515.

Example 6 Preparation of[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]-2-methylpropyl2-(3,3-diphenylprop-2-enylene)malonate (Via Route 1)

First Step: Preparation of2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propylMalonate

A solution of dimethylallyl malonate (10 g, 0.047 mol) and of catalyst(complex containing 3-3.5% by weight of Pt in cyclovinylmethylsiloxanefrom Hüls Petrarch PC085: 200 μl) in 30 ml of toluene is heated to 80°C. 23 g (0.104 mol) of heptamethyltrisiloxane are added dropwise theretoover 20 minutes. The mixture is heated at 80° C. for 16 hours. Thesolvent and the excess heptamethyltrisiloxane are evaporated off undervacuum.Bis[2-methyl-3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]malonateis thus obtained in the form of an oil, which is used without furtherpurification for the following step.

Second Step: Preparation of the Derivative of Example 6

A mixture of the above derivative (1 g, 0.00234 mol) and ofβ-phenylcinnamaldehyde (0.487 g, 0.00234 mol) in 20 ml of toluene, inthe presence of 0.1 ml of piperidine and 0.06 ml of acetic acid, isrefluxed for 12 hours. The reaction mixture is concentrated and theresidue is chromatographed on silica (eluent: 50/50 heptane/CH₂Cl₂) togive 0.62 g of the derivative of Example 6 (yield: 32%) in the form of apale yellow oil:

UV (Ethanol) λ_(max)=330 nm, ε_(max)=28 650, E1%=346.

Example 7 Preparation of Ethyl4,4-diphenyl-1,3-diene-N-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]-2-(4,4-diphenylprop-2-ethylene)malonamide(Via Route 2)

First Step: Preparation of EthylN-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propyl]malonamide

Malonic acid monoethyl ester chloride (3.3 g, 0.025 mol) is addeddropwise at 10° C. over 30 minutes to a mixture of3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]disiloxanyl]propylamine(6.99 g, 0.025 mol) and of triethylamine (2.2 g, 0.0275 mol) in 20 ml ofdichloromethane. The reaction mixture is allowed to warm to roomtemperature and is refluxed for two hours. The reaction mixture ispoured into 40 ml of water and is extracted with dichloromethane. Theorganic phases are washed with water and dried over sodium sulfate, andthe solvent is then evaporated off. After purification by passingthrough a column of silica (eluent: 95/5 CH₂Cl₂/methanol), 2.1 g of acolorless oil are obtained, and are used without further purification inthe following step.

Second Step: Preparation of the Derivative of Example 7

A mixture of the above derivative (1 g, 2.54×10 mol) and ofphenylcinnamaldehyde (0.53 g, 2.54×10 mol) is dissolved in 30 ml ofisopropyl alcohol, in the presence of 0.1 ml of piperidine, and ismaintained at 50° C. for three hours. The reaction mixture isconcentrated and the residue is chromatographed on silica (eluent: 80/20heptane/ethyl acetate) to give 1.22 g (82% yield) of the derivative ofExample 7 in the form of a pale yellow oil:

UV (Ethanol) λ_(max)=335 nm, ε_(max)=31 650, E1%=542.

COMPOSITION EXAMPLES

Composition A: Concentration Phase Constituents (g %) A Glycerylmonostearate/polyethylene glycol 1 stearate (100 EO) mixture (Arlacel165 - Uniqema) Fatty acids of plant origin (Stearine TP 1200 - 1.5Stéarineries Dubois) Dimethicone (Dow Corning 200 Fluid 350 0.5 CS - DowCorning) Cetyl alcohol (Lanette 16 - Cognis) 0.5Cetylstearylglucoside/cetylstearyl alcohol 2 mixture (Montanov 68 -SEPPIC) C₁₂-C₁₅ alkyl benzoate (Finsolv TN - Witco) 10 Compound ofExample 1 5 B Glycerol (Pricerine 9091 - Uniqema) 5 Hexadecyl phosphate,potassium salts 1 (Amphisol K - Roche Vitamins) EDTA 0.1 C Xanthan gum(Keltrol T - CP Kelco) 0.2 Acrylates/C₁₀-C₃₀-alkylacrylate crosslinked0.2 copolymer (Pemulen TR-1 - Noveon) Isohexadecane (Isohexadecane - BP)1 Triethanolamine qs pH Preservatives qs Demineralized water qs 100 g

Laboratory Manufacturing Protocol:

The fatty phase (A) is weighed out and heated on a water bath at 70° C.The aqueous phase (B) is weighed out in the final beaker and heated on awater bath at 70° C. The fatty phase is dispersed in the aqueous phasewith stirring using a Moritz rotor/stator stirrer (about 1000 rpm). Themixture of thickeners (C) is incorporated and the resulting mixture isallowed to cool to room temperature with stirring. At about 30° C., theformulation is neutralized and packaged. Composition B: ConcentrationPhase Constituents (g %) A Glyceryl monostearate/polyethylene glycol 1stearate (100 EO) mixture (Arlacel 165 - Uniqema) Fatty acids of plantorigin (Stearine TP 1.5 1200 - Stéarineries Dubois) Dimethicone (DowCorning 200 Fluid 350 0.5 CS - Dow Corning) Cetyl alcohol (Lanette 16 -Cognis) 0.5 Cetylstearylglucoside/cetylstearyl alcohol 2 mixture(Montanov 68 - SEPPIC) C₁₂-C₁₅ alkyl benzoate (Finsolv TN - 10 Witco)Compound of Example 3 5 B Glycerol (Pricerine 9091 - Uniqema) 5Hexadecyl phosphate, potassium salts 1 (Amphisol K - Roche Vitamins)EDTA 0.1 C Xanthan gum (Keltrol T - CP Kelco) 0.2Acrylates/C₁₀-C₃₀-alkylacrylate crosslinked copolymer (Pemulen TR-1 -Noveon) 0.2 Isohexadecane (Isohexadecane - BP) 1 Triethanolamine qs pHPreservatives qs Demineralized water qs 100 g

Laboratory Manufacturing Protocol:

The fatty phase (A) is weighed out and heated on a water bath at 70° C.The aqueous phase (B) is weighed out in the final beaker and heated on awater bath at 70° C. The fatty phase is dispersed in the aqueous phasewith stirring using a Moritz rotor/stator stirrer (about 1000 rpm). Themixture of thickeners (C) is incorporated and the resulting mixture isallowed to cool to room temperature with stirring. At about 30° C., theformulation is neutralized and packaged.

Each patent, patent application, publication and literaturearticle/report cited or indicated herein is hereby expresslyincorporated by reference.

While the invention has been described in terms of various specific andpreferred embodiments, the skilled artisan will appreciate that variousmodifications, substitutions, omissions, and changes may be made withoutdeparting from the spirit thereof. Accordingly, it is intended that thescope of the present invention be limited solely by the scope of thefollowing claims, including equivalents thereof.

1. A 4,4-diarylbutadiene-substituted diorganopolysiloxane having thestructural formulae (1) or (2):

in which A is a radical of formula (3) below:

in which the radicals R₁, which may be identical or different, are eacha hydroxyl radical, a saturated or unsaturated, linear or branchedC₁-C₁₀ alkyl radical, a saturated or unsaturated, linear or branchedC₁-C₁₀ alkoxy radical, with the proviso that two adjacent groups R₁ maytogether form a C₁-C₃ alkylenedioxy ring; n is an integer ranging from 0to 2; the radical Z is hydrogen, —(C═O)OR₂, —(C═O)R₃, —(C═O)NR₄R₅,—SO₂R₆, —CN or —(C═O)—X-L; X is —O— or —NR₄—; L is a divalent radicalattaching the radical A to the silicone chain and corresponding to oneof the formulae (a), (a′) or (a″) below:

in which W is a saturated or unsaturated, linear or branched C₁-C₆alkylene radical, optionally substituted with a hydroxyl radical or asaturated or unsaturated, linear or branched C₁-C₈ alkyl radical; Y is ahydrogen atom, a hydroxyl radical or a saturated or unsaturated, linearor branched C₁-C₈ alkyl radical; p is 0 or 1; the radicals R, which maybe identical or different, are each a saturated or unsaturated, linearor branched C₁-C₂₀ alkyl radical, a phenyl radical, a3,3,3-trifluoropropyl radical or a trimethylsilyloxy radical, at least80% in numerical terms of the radicals R being methyl radicals; theradicals B, which may be identical or different, are each a radical R ora radical A; r is a number ranging from 0 to 50; s is a number rangingfrom 0 to 20 and, if s is 0, at least one of the two radicals B is aradical A; u is a number ranging from 1 to 6 inclusive; t is a numberranging from 0 to 10; t+u is greater than or equal to 3; the radical R₂is hydrogen or a saturated or unsaturated, linear or branched C₁-C₂₀alkyl radical; the radical R₃ is a saturated or unsaturated, linear orbranched C₁-C₂₀ alkyl radical or a C₆-C₁₂ aryl radical; the radicals R₄and R₅, which may be identical or different, are each hydrogen or asaturated or unsaturated, linear or branched C₁-C₂₀ alkyl radical; andthe radical R₆ is a saturated or unsaturated, linear or branched C₁-C₂₀alkyl radical or a C₆-C₁₂ aryl radical, with the proviso that when twogroups (C═O)—X-L- are present, L is bonded to only one group A or B offormula (1) or (2), or mixture thereof.
 2. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, having the structural formula (1).
 3. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, having the structural formula (2).
 4. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), Z is a hydrogen atom.
 5. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), Z is —(C═O)R₂.
 6. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), Z is —(C═O)R₃.
 7. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), Z is —(C═O)NR₄R₅.
 8. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), Z is —SO₂R₆.
 9. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), Z is —CN.
 10. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), Z is —(C═O)—X-L-.
 11. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), X is —O—.
 12. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), X is —NR₄—.
 13. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), L is a divalent radical.
 14. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), L is a divalent radical (a′).
 15. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formula (3), L is a divalent radical (a″).
 16. The4,4-diarylbutadiene-substituted diorganopolysiloxane as defined by claim1, wherein formulae (1) or (2) and (3): the radical Z is —(C═O)R₃, —CNor —(C═O)—X-L-; R₃ is a C₁-C₄ alkyl radical; R is a C₁-C₄ alkyl radical;B is a C₁-C₄ alkyl radical; r ranges from 0 to 10 inclusive; s rangesfrom 0 to 6 inclusive; t+u ranges from 3 to 5; n is 0; W is CH₂; p is 1;Y is H or CH₃.
 17. The 4,4-diarylbutadiene-substituteddiorganopolysiloxane as defined by claim 1, having the structuralformula of compound A:


18. The 4,4-diarylbutadiene-substituted diorganopolysiloxane as definedby claim 1, having the structural formula of compound B:


19. The 4,4-diarylbutadiene-substituted diorganopolysiloxane as definedby claim 1, having the structural formula of compound C:


20. The 4,4-diarylbutadiene-substituted diorganopolysiloxane as definedby claim 1, having the structural formula of compound D:


21. The 4,4-diarylbutadiene-substituted diorganopolysiloxane as definedby claim 1, having the structural formula of compound E:


22. The 4,4-diarylbutadiene-substituted diorganopolysiloxane as definedby claim 9, wherein formulae (1) or (2) and (3): R is a C₁-C₄ alkylradical; B is a C₁-C₄ alkyl radical; r ranges from 0 to 10 inclusive; sranges from 0 to 6 inclusive; t+u ranges from 3 to 5; n is 0, W is CH₂,p is 1, Y is H or CH₃.
 23. The 4,4-diarylbutadiene-substituteddiorganopolysiloxane as defined by claim 1, having the structuralformula of compound F:


24. The 4,4-diarylbutadiene-substituted diorganopolysiloxane as definedby claim 1, having the structural formula of compound G:


25. The 4,4-diarylbutadiene-substituted diorganopolysiloxane as definedby claim 1, having the structural formula of compound H:


26. The 4,4-diarylbutadiene-substituted diorganopolysiloxane as definedby claim 1, having the structural formula of the mixture of compounds I:


27. The 4,4-diarylbutadiene-substituted diorganopolysiloxane as definedby claim 1, having the structural formula of compound J:


28. A topically applicable cosmetic/dermatological photoprotectivecomposition, comprising an effective UV-A photoprotecting amount of atleast one 4,4-diarylbutadiene-substituted diorganopolysiloxane asdefined by claim 1, formulated into a topically applicable,cosmetically/dermatologically acceptable support therefor.
 29. Thephotoprotective composition as defined by claim 28, said at least one4,4-diarylbutadiene-substituted diorganopolysiloxane comprising from0.01% to 20% by weight thereof.
 30. The photoprotective composition asdefined by claim 28, said at least one 4,4-diarylbutadiene-substituteddiorganopolysiloxane comprising from 0.1% to 10% by weight thereof. 31.The photoprotective composition as defined by claim 28, furthercomprising at least one additional UV-A and/or UV-B organic or mineralphotoprotecting active agent.
 32. The photoprotective composition asdefined by claim 31, comprising at least one additional organicphotoprotecting active agent selected from the group consisting ofanthranilates; cinnamic derivatives; dibenzoylmethane derivatives;salicylic derivatives; camphor derivatives; triazine derivatives;benzophenone derivatives; β,β-diphenylacrylate derivatives;benzotriazole derivatives; benzalmalonate derivatives; benzimidazolederivatives; imidazolines; bis-benzazolyl derivatives; p-aminobenzoicacid (PABA) derivatives; methylenebis(hydroxylphenylbenzotriazole)derivatives; benzoxazole derivatives; screening polymers and screeningsilicones other than those of formula (1) or (2); α-alkylstyrene-baseddimers; non-siliceous 4,4-diarylbutadienes, and mixtures thereof. 33.The photoprotective composition as defined by claim 32, comprising atleast one additional organic photoprotecting active agent selected fromthe group consisting of: Ethylhexyl salicylate, Ethylhexylmethoxycinnamate, Butyl methoxydibenzoylmethane, Octocrylene,Phenylbenzimidazolesulfonic acid, Benzophenone-3, Benzophenone-4,Benzophenone-5, n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,4-Methylbenzylidenecamphor, Terephthalylidenedicamphorsulfonic acid,Disodium phenyldibenzimidazoletetrasulfonate, 2,4,6-Tris(diisobutyl4′-aminobenzalmalonate)-s-triazine, Anisotriazine, Ethylhexyltriazone,Diethylhexylbutamidotriazone,Methylenebis(benzotriazolyl)tetramethylbutylphenol, Drometrizoletrisiloxane, Polysilicone-15,1,1-Dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene, 2,4-Bis[5-1(dimethylpropyl)benzoxazol-2-yl(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine,and mixtures thereof.
 34. The photoprotective composition as defined byclaim 31, comprising at least one additional mineral photoprotectingactive agent selected from the group consisting of coated or uncoatedmetal oxide pigments or nanopigments.
 35. The photoprotectivecomposition as defined by claim 34, said coated or uncoated metal oxidepigments or nanopigments comprising those of titanium oxide, zinc oxide,iron oxide, zirconium oxide, cerium oxide, and mixtures thereof.
 36. Thephotoprotective composition as defined by claim 28, further comprisingat least one active agent for artificially tanning and/or browning ofthe skin.
 37. The photoprotective composition as defined by claim 28,further comprising at least one cosmetic/dermatological adjuvantselected from the group consisting of fatty substances, organicsolvents, ionic or nonionic thickeners, softeners, humectants,antioxidants, moisturizers, desquamating agents, free-radicalscavengers, antipollution agents, antibacterial agents,anti-inflammatory agents, depigmenting agents, propigmenting agents,opacifiers, stabilizers, emollients, silicones, antifoams, insectrepellents, fragrances, preservatives, anionic, cationic, nonionic,zwitterionic or amphoteric surfactants, substance P antagonists,substance CGRP antagonists, fillers, pigments, polymers, propellants,and acidifying or basifying agents.
 38. The photoprotective compositionas defined by claim 28, formulated for UV-photoprotecting the humanepidermis as a nonionic vesicular dispersion, an emulsion, a cream, amilk, a gel, a cream-gel, a suspension, a dispersion, an oil, a powder,a solid tube, a mousse or a spray.
 39. The photoprotective compositionas defined by claim 28, formulated as a UV-photoprotecting makeup forthe eyelashes, the eyebrows, the nails or the skin and comprising ananhydrous or aqueous solid or paste, or emulsion, suspension ordispersion.
 40. The photoprotective composition as defined by claim 28,formulated for UV-photoprotecting the hair as a shampoo, a lotion, agel, an emulsion or a nonionic vesicular dispersion.
 41. AUV-photostable synthetic polymer or optical lens comprising an effectiveUV-A photostabilizing amount of at least one4,4-diarylbutadiene-substituted diorganopolysiloxane as defined byclaim
 1. 42. A regime or regimen for UV-photoprotecting human skinagainst the damaging effects of UV-A radiation, comprising topicallyapplying thereon a thus effective amount of the photoprotectivecomposition as defined by claim
 28. 43. A photostable, solvent-solubletopically applicable cosmetic/dermatological photoprotective compositionresistant to water and to perspiration, comprising an effective UV-Aphotoprotecting amount of at least one 4,4-diarylbutadiene-substituteddiorganopolysiloxane as defined by claim 1, formulated into a topicallyapplicable, cosmetically/dermatologically acceptable support therefor.